Anthracene-2.1-thioindoxyl and process of making the same



Patented Aug. 31, 1926.

UNITED STATES PATENT OFFICE.

ROBERT STOCKER, OF BASEL, AND JACOB MULLER, OF MUNCHENSTEIN, NEAR BASEL,SWITZERLAND, ASSIGNOBS TO SOCIETY OF CHEMICAL INDUSTRY IN BASLE, OF

BASE-L, SWITZERLAND.

ANTHRACENE-flJ-THIOINDOXYL AND PROCESS OF MAKING THE SAME.

Nb Drawing.

It has been found that a new anthracenethioindoxyl derivative may beobtained as follows:

First condensing the Q-mercaptO-anthra cene with monohalogeno aceticacids, such as monochloroor monobromo acetic acids to the2-anthracene-thioglycolic acid, then converting the latter into thecorresponding halide by treatment with a halide of an inorganic hydroxyacid, such as P01 or S001 and finally condensing the halide of the,.2-anthracene-thioglycolic acid thus obtained to theanthracene-2zl-thioindoxyl by means of condensing agents having an acidaction, such as A101 FeCl, ZnCl etc.

The new indoxyl corresponds with the formula:

It forms a yellow powder, insoluble in water, soluble in dilute alkaliesand the ordinary solvents, such as alcohol, acetone, benzene, etc.Crystallized from dilute alcohol it forms yellow needles melting at 172.

Ewa'mple.

21 parts of 2-mercapto-anthracene corresponding with the formula:

are dissolved at 80 C. in 1000 parts of water and 40 parts of causticsoda of 30% strength and treated with an exactly neutralized solution of11 parts of monochloroacetic acid. The mixture is heated for some timeat 7080, whereby the original orange Application filed January 4, 1926,Serial No. 79,228, and in Switzerland January 14, 1925.

coloration of the solution turns over to pale yellow. At the same timethe sodium salt of anthracenethioglycolic acid begins partly toprecipitate. The condensation being achieved, the hydrochloric acid isadded to the mixture whereby the free 2-anthracenethioglycolic acidcorresponding with the formula:

precipitates in yellowish white flakes. Crystallized once from benzene,the new product forms yellow needles melting at 105.

26.8 parts of Q-anthracenethioglycolic acid are triturated with 22 partsof phosphorus pent-a-chloride. The mass liquefies with strong evolutionof hydrochloric acid gas. The whole is allowed to rest for 15-30 minutesin a reflux apparatus on the boiling water bath until the formation ofthe acid chloride is achieved. The phosphorus oxychloride is thendistilled ofi in a vacuum and the Q-anthracenethioglycolic acid chloridemixed with 150 parts of chlorobenzene. To this solution 21.5 parts ofaluminium chlo ride are added, whereby its coloration turns over to red.The whole is heated for some hours until the evolution of hydrochloricacid is completed. The reaction product is introduced into a mixture ofice and hydrochlonic acid and the solvent is distilled off with steam.The 2:1-anthracene thioindoxyl of the formula:

residue with hot dilute caustic soda solution. The new compound iscrystallized from dilute alcohol.

What we claim is 1. As step in the production of anthracene-2:1-thioindoxy1 the condensation of the 2- mercaptoanthracene withmonohalogenoacetic acids to the 2-anthracencthioglycolic acid.

2. As step in the production of anthracene- 2:1-thioindoxyl theconversion of the an thraccne-Q-thioglycolic acid to the halide of theanthi'acene-Q-thioglycolic acid by treatment with halides of inorganichydroxy acids.

3. As step in the production of anthl'acene 2:1-thioindoxyl thetreatment of the anthraccnc-2-thi0glycolic acid halide with condensingagents having an acid action.

4. As new product the herein described new anthracene-2:l-thioindoxylcorresponding with the formula:

0=C C=H1 which product forms a yellow powder, insoluble in water,soluble in dilute alkalies and in alcohol, acetone and benzene,crystallizing from dilute alcohol forming yellow needles melting at 1T2C.

In witness whereof we have hereunto signed our names this 19th day ofDecember, 1925.

ROBERT STOCKER. JACOB MULLER.

residue with hot dilute caustic soda solution. The new compound iscrystallized from dilute alcohol.

\Vhat we claim is z- 1. As step in the production of anthracene-2:1-thioindoxyl the condensation of the 2- mercaptoanthracene withmonohalogenoacetic acids to the 241nthracenethioglycolic acid.

2. As step in the production of anthracene- 2:1-thioindoxyl theconversion of the anthraccne-Q-tliioglycolic acid to the halide of theanthracene-Q-thioglycolic acid by treatment with halides of inorganichydroxy acids.

3. As step in the production of anthracene- 2:1-thioindoxyl thetreatment of the anthracene-fi-thioglycolie acid halide with con-(lensing agents having an acid action.

4. As new product the herein described new anthracene-2:l-thioindoxylcorresponding with the formula:

which product forms a yellow powder, insoluble in water, soluble indilute alkalics and in alcohoL acetone and benzene, crystullizing fromdilute alcohol forming yellow needles melting at 172 C.

In witness whereof we have hereunto signed our names this 19th day ofDecember, 1925.

ROBERT STOCKER. JACOB MULLER.

Certificate of Correction.

Patent No. 1,598,167, granted August 31, 1926, to

ROBERT STOCKER, of Basel, and JACOB MULLER, of Munchenstein, near Basel,Switzerland.

It is hereby certified that error appears in the printed specificationof the abovementloned patent requiring correction as follows: Page 1,lines 1824, strike out the present formula and insert instead and thatthe said Letters Patent should be read with this correction therein thatthe same may conform to the record of the case in the Patent Office.

Signed and sealed this 1st day of March, A. D. 1927.

[SEAL] M. J. MOORE, Acting Gammeksioner of Patents.

Certificate of Correction.

Patent No. 1,698,167, granted August 31, 1926, to

ROBERT STOCKER, of Basel, and JACOB MULLER, of Munchenstein, near Basel,Switzerland.

It is hereby certified that error appears in the printed specificationof the abovementioned patent requlring correction as follows: Page 1,lines 1824, strike out the present formula and insert instead O=C-C=H:

and that the said Letters Patent should be rear] with this correctiontherein that the same may conform to the record of the case in thePatent Oflice.

Signed and sealed this 1st day of March, A. D. 1927.

[SEAL] M. J. MOORE,

Acting Commissioner of Patent.

